Functional sugar substitutes with reduced calories

ABSTRACT

Disclosed are novel 5-C-hydroxymethylhexose compounds and their derivatives which exhibit sugar-like functionality when used in food compositions. The derivatives include stereoisomers, di-, tri-, and polysaccharides, alkyl glycosides, polyol, and alditol derivatives. Also disclosed are sugar substitute compositions and food compositions containing these compounds and their derivatives.

This is a division of application Ser. No. 07/653,331, filed on Feb. 11,1991, now U.S. Pat. No. 5,041,541, issued Aug. 20, 1991, which is adivision of application Ser. No. 07/339,531, filed on Apr. 20, 1989, nowU.S. Pat. No. 5,064,672, issued Nov. 12, 1991, which is acontinuation-in-part of Ser. No. 190,486, filed May 5, 1988, nowabandoned.

TECHNICAL FIELD

This invention relates to novel 5-C-hydroxymethyl hexose-based compoundsand their use as sugar substitutes. These carbohydrates providesugar-like functionality while having significantly reduced caloriescompared to sucrose. This invention also relates to food and beveragecompositions which include these carbohydrates.

BACKGROUND OF THE INVENTION

The ready availability of a variety of highly flavorful foods coupledwith the relatively sedentary lifestyles of a portion of the populationhas resulted in an accumulation of calories in these people. Estimatesindicate that currently as much as 40% of the U.S. population isoverweight. J. J. Beereboom, CRC Critical Reviews in Food Science andNutrition, 11(4), pps. 401-413, May 1979. Consequently, an increasingnumber of people are practicing some form of dieting and/or monitoringof caloric intake. This has led to the successful introductions andrapid growth of a variety of reduced calorie food products, such as cakemixes, beers, wines, candies and sodas.

Two of the most significant contributors to the population's caloricintake are sucrose (i.e., common table sugar) and high fructose cornsyrup. In fact, a great deal of effort has been expended to develop afunctional reduced calorie sugar substitute.

In 1985, the Calorie Control Council's brochure Sweet Choices describedthe ideal sweetener as having the following characteristics:

same or greater sweetness as sucrose

colorless

odorless

readily soluble in water

stable

functionally similar to sucrose

economically feasible

contribute reduced or no calories to the diet

non-toxic and non-promoting of dental caries

The Council commented that up to that date a sweetener having all thosecharacteristics did not exist.

Sugars are best known as sweeteners, however, their role as functionalcomponents in foods is equally important. Sugar influences many foodproperties in addition to flavor. It alters the degree of hydration ofmany substances, influences the viscosity of starch pastes, the firmnessof gelatin and pectin gels, and the formation and strength of glutenstrands. It controls the gelatinization temperature of starch and thegelation temperatures of gluten and egg proteins. It affects the rate ofspoilage due to the growth of micro-organisms. In many cases, it altersthe color and texture of fruit products. It increases themoisture-retaining ability of many foods. The size of sugar crystalsinfluences markedly the textural characteristics of candies andfrostings, and it enhances the body of beverages. (See Paul and Palmer,Food Theory and Applications, pg. 47 (1972)). The concentration of sugarin the food product regulates the properties. As a result, the volumefraction of sugar in foods is often very high. This is commonly referredto as sugar's bulking characteristic. One of the major problems indeveloping a reduced calorie sugar substitute is to provide this bulkingcharacteristic.

Most artificial sweeteners in use today have a greater relativesweetness than sucrose; thus, relatively small quantities are requiredto deliver the desired sweetness. Such low volume sweeteners may beacceptable for certain applications (e.g., beverages), however, they donot provide sufficient bulk and functionality for use in solid andsemi-solid foods like baked goods and frozen desserts. In fact, evenhigh intensity sweetener-containing beverages have a detectablereduction in their body. Two avenues have been explored to overcome thisbulking problem:

combinations of bulk extenders and available artificial sweeteners

modified sugars

Presently-available sweeteners and sweetener/bulk extender combinationsare not satisfactory due to their significant deviation from theimportant functional characteristics of sucrose (e.g., solubility andcontrol of starch gelatinization), significant caloric values, andnegative physiological effects.

Polydextrose, produced by Pfizer Corp., is a non-sweet, randomly bondedglucan containing small amounts of sorbitol and citric acid. It ispresently the most widely used reduced calorie bulk extender in foods.As a sugar substitute it contributes 1 kcal/g, which is equivalent toabout 25% of the caloric contribution of sucrose. Unfortunately,polydextrose has a low laxative threshold and has little control ofstarch gelatinization. See Food Technology, January 1986, "SpecialReport: Sweeteners and Product Development", pg. 129.

U.S. Pat. No. 2,876,105, Jucaitis and Biudzius, issued Mar. 3, 1959,discloses another class of carbohydrate polymers to be used as bulkextenders. Other bulk extenders include gum arabic and gum tragacanth.However, they are not desirable since they are not readily soluble,especially in cold liquids, and they have high relative viscosities andthey have little control of starch gelatinization. See U.S. Pat. No.3,704,138, LaVia, issued Nov. 28, 1972.

Arabinogalactan (Larch Gum) is a highly branched polymer of arabinoseand galactose obtained from the Western Larch tree. Though it has FDAclearance for use in foods and has many suitable physical properties,such as good solubility in solutions having low viscosities, actual usehas been small due to taste, functional, heat-stability problems andpoor starch gelatinization control.

U.S. Pat. No. 4,207,413, Szarek et al., issued June 10, 1980, disclosesthat L-sucrose (α-L-glucopyranosyl-β-L-fructofuranoside) has identicalsweetness to sucrose but is not metabolized on ingestion and is,therefore, non-caloric. The high cost of synthesizing this compound actsas a significant barrier to its development as a dietary sweeteningagent. See Kirk-Othmer, Encyclopedia of Chemical Technology, third ed.,Vol. 21, pg. 939 (1978). A later patent discloses that L-monosaccharidesare also edible and non-caloric (U.S. Pat. No. 4,262,032, Levin, issuedApr. 14, 1981). These L-sugars are also very costly to synthesize.

Sugar alcohols, called alditols, have also been proposed as sugarsubstitutes. However, only a few alditols have been approved as foodadditives and they have limited dietary applications due to their lowlaxative threshold and significant caloric value. (See, Rothschild, FoodChemical News Guide, mannitol, pg. 255 (1987); sorbitol, pg. 430 (1982);xylitol, pg. 495 (1986)).

In order to test structure-sweetness correlations, Witczak and Whistler,Carbohydrate Research, 169 (1987), 252-257, synthesized a large group ofcompounds including the branched chain alditol,2-C-(hydroxymethyl)-D-mannitol. Witczak and Whistler did not comment onthe metabolizability of the compound.

U.S. Pat. No. 4,459,316, Bakal, issued July 10, 1984, teaches that di-and trisaccharides containing one levohexose component and at least onedextrohexose component (e.g., α-L-glucopyranosyl-D-fructofuranose) arenon-caloric. These disaccharides are costly to synthesize due to thefact that they are prepared from a racemic mixture of D-hexoses andexpensive L-hexoses.

Thus, a sugar replacement which is low in calories, inexpensive tosynthesize, sweet, functional (especially as a bulking agent) and avoidsnegative physiological effects is highly desirable.

It has now been found, that carbohydrates in the5-C-hydroxymethyl-hexose series can be effectively used as replacementsfor sugar, especially in baked goods. These carbohydrate derivativesprovide sucrose-like functionality (i.e., bulk, texture and stability)with significantly reduced calories compared with sucrose. In addition,many of these carbohydrate derivatives are easier to synthesize thancurrently available functional sugar substitutes. It is believed thatthey are essentially free of the significant negative physiologicaleffects (i.e., flatus and diarrhea) generally associated with suchcompounds. It has also been shown that saccharides containing a5-C-hydroxymethyl-hexose component provide similar benefits. This alsoholds true for the alditols of these carbohydrates (e.g.,5-C-hydroxymethyl-hexitols, 5-C-hydroxymethyl-aldohexosyl polyolderivatives, alkyl derivatives (e.g., 5-C-hydroxymethyl-aldohexosylglycerol and 5-C-hydroxymethyl-aldohexosyl-glucitol) of thecarbohydrates (i.e., alkyl 5-C-hydroxymethyl-aldohexosides), and1,6-anhydro-β-L-, and 1,6-anhydro-β-D derivatives of the pyranosecompounds (i.e., the bicyclic tautomeric forms) and the relatedderivatives of the ketohexoses.

SUMMARY OF THE INVENTION

The novel carbohydrates of the present invention encompass5-C-hydroxymethyl-hexose monosaccharides, and several specificderivatives. The carbohydrates include 5-C-hydroxymethyl derivatives ofallose, -altrose, -glucose, -mannose, -gulose, -idose, -galactose,-talose, -fructose, -psicose, -sorbose and -tagatose in their D or Lconfiguration and as the α or β anomer. These carbohydrates include thestraight-chain, pyranose and furanose tautomeric forms. The specificnovel derivatives of 5-C-hydroxymethyl-aldohexose include1,6-anhydro-β-L-aldohexoses, 1,6-anhydro-β-D-aldohexoses, alkyl5-C-hydroxymethyl-aldohexosides and polyols derived from5-C-hydroxymethyl-aldohexosyl compounds. Also included are alkyl5-C-hydroxymethyl-ketohexosides and polyols derived from5-C-hydroxymethyl-ketohexosyl compounds.

The invention also comprises novel di-, tri-, oligo- and polysaccharidescontaining at least one simple sugar linkage from the above-mentionednovel carbohydrates.

The invention also encompasses sugar substitute compositions, providingnearly identical sweetness and bulk when compared to sucrose, whichcomprise the novel carbohydrates or their alditols blended withconventional artificial sweeteners or with mixtures of conventionalsugars and artificial sweeteners, and, optionally conventional bulkingagents.

The invention further encompasses food compositions (e.g., beverages,baked goods, frozen deserts and candies) containing the above-mentionednovel carbohydrates or their alditols.

Other novel food compositions of the present invention includefat-containing foods containing the above-mentioned carbohydrates ortheir alditols in combination with polyol polyesters.

DETAILED DESCRIPTION OF THE INVENTION

All ratios and percents described herein are "by weight" unlessotherwise specified.

DEFINITIONS

The term "baked goods" refers to all manner of foods which are cooked(i.e., prepared using heat). These baked goods include, but are notlimited to, foods prepared using dry heat (i.e., a radiant or convectionoven), fried foods, boiled foods and foods heated in a microwave oven.

The term "food compositions" refers to and includes all manner of viand(both sweetened and un-sweetened foods) for usage by man or animal.These food stuffs include, but are not limited to, baked goods, saltedsnacks, other flavored snacks, fruit drinks/mixes, frozen foods,candies, carbonated beverages, milk drinks/mixes, gelatins, puddings,fillings, breakfast cereals, breakfast bars, sauces, jams, jellies,whipped toppings, tablets, syrups, orally administered medicines,spreads, chewing gums and chocolates.

The term "galactose oxidase" as used herein refers to D-galactose:oxygen 6-oxidoreductase which is identified as E.C. 1.1.3.9 or asChemical Abstracts Registry Number 9028-79-9.

The term "catalase", as used herein, refers to H₂ O₂ :H₂ O₂oxidoreductase which is identified as E.C. 1.11.1.6. Catalase is anoxidizing enzyme which decomposes hydrogen peroxide. These enzymes occurin both plant and animal cells.

The term "bulking compound" as used herein refers to a compound whichprovides acceptable bulk (i.e., displacement) and similar functionalitywhen compared with sucrose in food composition applications.

The term "sweetening compound" as used herein refers to a compound whichproduces a sweet sensory response. Sweetening compounds include, but arenot limited to: sucrose, glucose, fructose, lactitol, maltitol,sorbitol, alitame, sucralose, acesulfame, aspartame, cyclamates,saccharin and mixtures of these compounds. The term "sweeteningcompound" does not refer to any of the novel compounds described hereinor their alditols.

The term "sugar substitute" as used herein refers to a composition whichis effective in replacing conventional sugars (i.e., sucrose, fructose,glucose, etc.) in food compositions and provides sugar-likefunctionality in the form of degree of hydration, viscosity, color,texture, odor, presentation and bulk, but with significantly reducedcalories.

The term "hexose" means a carbohydrate containing six carbons. This termencompasses both aldehyde containing hexoses (aldohexoses) and ketonecontaining hexoses (ketohexoses).

The term "aldohexoses" refers to the group of sugars whose moleculecontains six carbon atoms, one aldehyde group and five alcohol groups.The sixteen stereoisomers of the aldohexose series are D-allose,D-altrose, D-glucose, D-mannose, D-gulose, D-idose, D-galactose,D-talose, L-allose, L-altrose, L-glucose, L-mannose, L-gulose, L-idose,L-galactose and L-talose. These sugars exist in solution as anequilibrium mixture of several "tautomeric forms": a pyran-ring form; afuran-ring form; or a straight-chain aldehyde form. Tautomeric forms ofD-glucose: ##STR1## Aldohexoses may also occur in an α or β anomericconfiguration, depending on the position of the C-1 hydroxyl group.Examples are: ##STR2##

The term "D-ketohexose" refers to the group of sugars which contain sixcarbon atoms, one ketone group and five alcohol groups. The eightstereoisomers are D- and L- isomers of psicose, fructose, sorbose andtagatose. Like the aldohexoses, these ketohexoses can exist in solutionas an equilibrium mixture of several "tautomeric forms": pyran-ring; afuran ring and a straight chain ketone form.

The terms "sugar derivatives" and "novel compounds" as used herein referto the 5-C-hydroxylmethyl derivatives of the hexose and theirstereoisomers and polymers which are the subject of this invention.

The term "polyol polyester" refers to sugar fatty acid polyesters orsugar alcohol fatty acid polyesters having at least 4 fatty acid estergroups with each fatty acid having from 8 to 22 carbon atoms. Suchpolyesters and their use in conventional food products have beendisclosed in, for example, U.S. Pat. No. 3,600,186, Mattson et al.,issued Aug. 17, 1971; U.S. Pat. No. 3,954,976, Mattson et al., issuedMay 4, 1976; U.S. Pat. No. 3,963,699, Rizzi et al, issued June 15, 1976;U.S. Pat. No. 4,005,195, Jandacek, issued Jan. 25, 1977; U.S. Pat. No.4,005,196, Jandacek et al., issued Jan. 25, 1977; and U.S. Pat. No.4,382,924, Berling et al., issued May 10, 1983.

The term "polyol" includes all polyhydric alcohols (i.e., thosecompounds of the general formula CH₂ OH(CHOH)_(n) CH₂ OH, where n may befrom 0 to 5.) glycerol contains three hydroxyl groups. Those with morethan three are called sugar alcohols.

DESCRIPTION OF THE NOVEL COMPOUNDS

The novel 5-C-hydroxymethylaldohexose monosaccharides of the presentinvention include the following: ##STR3##

5-C-hydroxymethylaldohexose (straight-chain)

The preferred embodiments of the straight-chain5-C-hydroxymethylaldohexose compounds are 5-C-hydroxymethyl derivativesof galactose, glucose, and mannose. Due to the relative ease ofsynthesizing galactose-based compounds, 5-C-hydroxymethyl derivatives ofD-galactose is the most preferred compound. ##STR4##

5-C-hydroxymethylaldohexopyranose

The preferred embodiments of the 5-C-hydroxymethylaldohexopyranosecompounds are 5-C-hydroxymethyl derivatives of galactopyranose,-glucopyranose, and -mannopyranose. Due to the relative ease ofsynthesizing galactose-based compounds, 5-C-hydroxymethyl derivative ofD-galactopyranose is the most preferred compound. ##STR5##

5-C-hydroxymethylaldohexofuranose

The preferred embodiments of the 5-C-hydroxymethylaldohexofuranosecompounds are 5-C-hydroxymethyl derivatives of galactofuranose,-glucofuranose, and -mannofuranose. Due to the relative ease ofsynthesizing galactose-based compounds, 5-C-hydroxymethyl derivative ofD-galactofuranose is the most preferred embodiment.

The novel 5-C-hydroxymethyl-aldohexose derivatives of this inventioninclude: ##STR6##

1,6-anhydro-5-C-hydroxymethyl-β-D-aldohexopyranose

The preferred embodiment of the1,6-anhydro-5-C-hydroxymethyl-β-D-aldohexopyranose compounds is1,6-anhydro-5-C-hydroxymethyl-β-D-galactopyranose. ##STR7##

1,6-anhydro-5-C-hydroxymethyl-β-L-aldohexopyranose

The preferred embodiments of the1,6-anhydro-5-C-hydroxymethyl-β-L-aldohexopyranose compounds are1,6-anhydro-5-C-hydroxymethyl-β-L-altropyranose, -gulopyranose andidopyranose. The most preferred embodiment is1,6-anhydro-5-C-hydroxymethyl-β-L-altropyranose. ##STR8##

alkyl 5-C-hydroxymethyl-aldohexopyranoside

The preferred embodiments of alkyl 5-C-hydroxymethylaldohexopyranosidesare ethyl and methyl 5-C-hydroxymethylaldohexopyranoside. The mostpreferred embodiment is ethyl D-galactopyranoside. ##STR9##

alkyl 5-C-hydroxymethylaldohexofuranoside

The preferred embodiments of alkyl 5C-hydroxymethylaldohexofuranosidesare ethyl and methyl 5-C-hydroxymethylaldohexofuranoside. The mostpreferred embodiment is ethyl 5-C-hydroxymethyl-L-arabinohexofuranoside.

(VIII) Another novel derivative of the present invention occurs when apolyol is covalently bound by a glycoside linkage to one of theabove-mentioned 5-C-hydroxymethylated saccharides. Preferred embodimentsof these compounds include: ##STR10##5-C-hydroxymethyl-α-L-arabino-hexopyranosyl-(1→1)-glycerol; ##STR11##5-C-hydroxymethyl-β-L-arabino-hexopyranosyl-(1→2)-glycerol; and##STR12## 5-C-hydroxymethyl-α-L-arabino-hexopyranosyl-(1→4)-D-glucitol(a lactitol derivative).

Other monosaccharides based on the ketohexose derivatives are: ##STR13##

Preferred embodiments are 5-C-hydroxymethyl derivatives of fructose andsorbose, including alkyl glycosides, due to the availability of naturalsugars.

The monosaccharides discussed above (I-XI) may also be classified assimple sugars. Simple sugar linkages are the building blocks for di-,tri-, oligo- and polysaccharides. The novel di-, tri-, oligo- andpolysaccharides of the present invention contain at least one simplesugar group (i.e., monosaccharides, monosaccharide derivatives) from themonosaccharides discussed above (I-XI) or their alditols covalentlybound through glycoside linkages to one or more simple sugar or simplesugar groups through any of the glycoside acceptor carbon positions(i.e., C-1 through C-7). The preferred glycoside linkages are through(C-1 and C-4.

Preferred disaccharides comprise at least one simple sugar linkageselected from the group consisting of 5-C-hydroxymethylaldohexose;1,6-anhydro-5-C-hydroxymethyl-β-D-aldohexopyranose;1,6-anhydro-5-C-hydroxymethyl-β-L-aldohexopyranose;5-C-hydroxymethylaldohexosyl polyol and alkyl5-C-hydroxymethylaldohexoside, where the alkyl group is selected fromthe group consisting of methyl, ethyl, propyl and isopropyl.

Other preferred disaccharides comprise at least one simple sugar linkageselected from the group consisting of 5-C-hydroxymethylketohexose;5-C-hydroxymethylketohexosyl polyol and alkyl5-C-hydroxymethylketohexoside wherein the alkyl group is selected fromthe group of methyl, ethyl, propyl and isopropyl.

The following disaccharides are most preferred compounds: ##STR14##5-C-hydroxymethyl-α-L-arabino-hexopyranosyl-(1→4)-D-glucopyranose;##STR15##5-C-hydroxymethyl-α-L-arabino-hexopyranosyl-(1→6)-D-galactopyranose;##STR16##5-C-hydroxymethyl-α-L-arabino-hexopyranosyl-(1→6)-(α+.beta.)-D-galactofuranose;and 5-C-hydroxymethyl-α-D-xylo-hexopyranosyl-β-D-fructofuranoside(asucrose derivative).

The preferred disaccharides containing 5-C-hydroxymethyl keto hexosesare:

KETOHEXOSE DERIVATIVES DISACCHARIDES ##STR17## (A)α-D-glucopyranosyl-5-C-hydroxymethyl-β-D-erythro-hexulofuranoside (B)5-C-hydroxymethyl-α-D-xylo-hexopyranosyl-5-C-hydroxymethyl-β-D-erythrohexulofuranoside

The preferred trisaccharides comprise at least one simple sugar linkageselected from the group consisting of 5-C-hydroxymethylaldohexose;1,6-anhydro-5-C-hydroxymethyl-β-D-aldohexopyranose;1,6-anhydro-5-C-hydroxymethyl-β-L-aldohexopyranose;5-C-hydroxymethylaldohexosyl polyol derivatives and alkyl5-C-hydroxymethyl-D-aldohexoside, where the alkyl is selected from thegroup consisting of methyl, ethyl, propyl and isopropyl. The mostpreferred trisaccharide embodiment is: ##STR18##5-C-hydroxymethyl-β-L-arabino-hexopyranosyl-α-D-glucosyl-β-D-fructofurnoside(a raffinose derivative).

Preferred oligosaccharides comprise at least one simple sugar linkageselected from the group consisting of 5-C-hydroxymethylaldohexose;1,6-anhydro-5-C-hydroxymethyl-β-D-aldohexopyranose;1,6-anhydro-5-C-hydroxymethyl-β-L-aldohexopyranose;5-C-hydroxymethylaldohexosyl polyol derivatives and alkyl5-C-hydroxymethylaldohexoside, where the alkyl group is selected fromthe group consisting of methyl, ethyl, propyl and isopropyl.

The most preferred oligosaccharide embodiment is: ##STR19##5-C-hydroxymethyl-α-D-galactosyl-α-D-galactosyl-α-D-glucosy-β-D-fructose(a stachyose derivative).

The preferred polysaccharides comprise at least one simple sugar linkageselected from the group consisting of 5-C-hydroxymethylaldohexose;1,6-anhydro-5-C-hydroxymethyl-β-D-aldohexopyranose;1,6-anhydro-5-C-hydroxymethyl-β-L-aldohexopyranose;5-C-hydroxymethylaldohexosyl polyol derivatives; alkyl5-C-hydroxymethylaldohexoside, 5-C-hydroxymethylketohexose,5-C-hydroxylmethylketohexosyl polyol derivatives and alkyl5-C-hydroxymethylketohexoside where the alkyl is selected from the groupconsisting of methyl, ethyl, propyl and isopropyl. Finally, the mostpreferred polysaccharide embodiment is an arabinogalactan derivativewherein at least one D-galactosyl component is replaced with a5-C-hydroxymethyl-α-L-arabinopyranosyl group.

USES OF THE NOVEL COMPOUNDS

The novel compounds described above and their alditols (i.e., hexitols)provide sugar-like functionality (i.e., degree of hydration, viscosity,color, texture, odor and bulk) with significantly reduced calories(often none) compared with conventional caloric sugars (e.g., sucrose,fructose, glucose, etc.). Several of these compounds also exhibit somesweetness (about 30% sucrose). In addition, these novel compoundsexhibit sugar-like characteristics when used in a wide range of foodcompositions. These novel compounds and their alditols are particularlyeffective in producing low calorie food compositions.

A. FOOD COMPOSITIONS

Novel food compositions of the present invention contain from about 1%to about 99% of any of the above-mentioned compounds. Preferredembodiments of these food compositions include baked goods, fruitdrinks/mixes, frozen foods, candies, carbonated beverages, milkdrinks/mixes, gelatins, puddings, fillings, breakfast cereals, breakfastbars, sauces, jams, jellies, whipped toppings, tablets, syrups, orallyadministered medicines, spreads, chewing gums and chocolates. The mostpreferred food compositions are baked goods.

Food compositions with reduced caloric value are often prepared bydirectly substituting one of the above-mentioned compounds for sucrosein a typical food formulation. Due to the natural variation of naturalraw materials, the ratio of ingredients may need to be varied by askilled food technologist.

Just as adjustments are made in recipes and formulations for thedifferent properties of sucrose and fructose or dextrose, adjustmentsfor the different properties of these sugar derivatives must be made.These changes are within the skill of one in the art.

The following is by way of example a partial list of food compositionswhich can be made with these sugar derivatives: cakes, cookies,brownies, other sweet snacks, icings, frostings, pie fillings, puddings,creams, hard and soft candies, chocolates, crackers, snacks made frompotatoes, corn, wheat and other grains, sauces gravies, yogurt,breadings, breads (some sugar must be added to make the yeast work),rolls, muffins, doughnuts and sweet rolls.

B. Sugar Substitutes

Several of the novel compounds and/or their alditols exhibit a lowsweetness intensity relative to sucrose. By using these compounds asbulking compounds in combination with a known sweetening compound ofhigher sweetening intensity, a composition which provides sucrose-likecharacteristics is produced (i.e., a sugar substitute). These sugarsubstitute compositions comprise from about 1% to about 99.99% of one ora mixture of the above-mentioned novel compounds and/or their alditolsand from about 0.01% to about 99% of a sweetening compound. Preferrednovel compound components include 5-C-hydroxymethylaldohexose;1,6-ahydro-5-C-hydroxymethyl-β-D-aldohexopyranose;1,6-anhydro-5-C-hydroxymethyl-β-L-aldohexopyranose;5-C-hydroxymethylaldohexosyl polyol derivatives; alkyl5-C-hydroxymethylaldohexoside, where the alkyl is selected from thegroup consisting of methyl, ethyl, propyl and isopropyl;5-C-hydroxymethylaldohexitols; di-, tri-, oligo- or polysaccharidescomprised from the above-mentioned simple sugars and mixtures of thesecompounds.

The most preferred novel compounds include5-C-hydroxymethyl-L-arabino-hexose; 5-C-hydroxymethyl-D-xylo-hexose;5-C-hydroxymethyl-D-lyxo-hexose1,6-anhydro-5-C-hydroxymethyl-β-L-altropyranose,1,6-anhydro-5-C-hydroxymethyl-β-L-idopyranose;1,6-anhydro-5-C-hydroxymethyl-β-L-gulopyranose; Methyl5-C-hydromethyl-arabino-hexoside; ethyl5-C-hydroxymethyl-L-arabino-hexoside;5-C-hydroxymethyl-L-arabino-hexosyl glycerol;5-C-hydroxymethyl-α-D-xylo-hexopyranosyl-β-D-fructofuranoside;5-C-hydroxymethyl-α-L-arabino-hexopyranosyl-(1→4)-D-galactopyranose;5-C-hydroxymethyl-α-L-arabino-hexopyranosyl-(1→6)-D-galactopyranose;5-C-hydroxymethyl-α-L-arabino-hexopyranosyl-α-D-glucosyl-D-fructose;5-C-hydroxymethyl-α-L-arabino-hexopyranosyl-D-galactosyl-α-D-glucosyl-α-D-fructose;5-C-hydroxymethyl-α-L-arabino-hexopyranosyl-D-glucitol; arabinogalactanderivatives whereby at least one galactosyl group is converted to a5-C-hydroxymethyl derivative; and mixtures thereof.

These sugar substitutes may further comprise from about 1% to about 99%of conventional bulking compound. Preferred conventional bulkingcompounds include polydextrose, arabinogalactan, gum arabic, gumtragacanth, locust bean gum, carrageenan, guar gum, agarose, or mixturesthereof.

Preferred sweetening compounds include sucrose, glucose, fructose,lactitol, maltitol, sorbitol, alitam, sucralose, acesulfame, aspartame,cyclamates, saccharin and mixtures of these compounds.

C. COMBINATIONS WITH ZERO OR LOW CALORIE FATS

The novel compounds or their polyols can also be used in combinationwith a polyol polyester compound to provide a food composition withnearly no caloric value. Low calorie fat containing food compositions ofthe present invention are those wherein from about 10% to about 100% ofthe total fat in the food composition consists of a polyol polyestercompound, and which comprise from about 1% to about 99% of one or amixture of the above-mentioned novel compounds or their alditols.Preferred polyol polyester compounds include glucose tetraoleate,glucose tetrastearate, glucose tetraester of soybean oil fatty acid,mannose tetraester of tallow fatty acid, galactose tetraester of oliveoil fatty acid, arabinose tetraester of cottonseed oil fatty acid,xylose tetralinoleate, galactose pentastearate, sorbitol tetraoleate,sorbitol hexaester of olive oil fatty acid, xylitol pentapalmitate,xylitol tetraester of substantially completely hydrogenated cottonseedoil fatty acid, sucrose tetrastearate, sucrose pentastearate, sucrosehexaoleate, sucrose octaester of substantially completely hydrogenatedsoybean oil fatty acid, sucrose octaester of peanut oil fatty acid,erythritol tetraester of olive oil fatty acid, erythritol tetraoleatexylitol pentaoleate, sorbitol hexaoleate, sucrose octaoleate, sucroseoctaester of soybean oil fatty acid and mixtures of these compounds.Sucrose fatty acid polyesters, wherein at least about 60% of thepolyesters are octaester are particularly preferred.

The very low degree of metabolism of the novel carbohydrate compoundsserves to reduce dental caries and to extend the shelf life of foodcompositions containing these compounds. Food compositions containingthese compounds are particularly useful in the treatment of diabetes.Drug compositions containing the above-mentioned compounds areparticularly efficacious where a low calorie level is critical or whereconventional sugars are deleterious.

It has recently been found (concurrently-filed U.S. patent applicationSer. No. 190,485, filed May 5, 1988 Mazur, Hiler, Stipp and Kluesener)that the 5-C-hydroxy methylation of D-aldohexose-based compounds can beaccomplished by a process which comprises an enzymic oxidation reactionfollowed by a condensation reaction with formaldehyde.

The preparation of the foregoing compounds and their use in foodcompositions and sugar substitutes is described in the followingexamples:

EXAMPLE I Preparation of methyl5-C-hydroxymethyl-α-L-arabino-hexopyranoside from methylβ-D-galactoside. 1. Oxidation of Methyl β-D-Galactopyranoside withGalactose Oxidase

    ______________________________________                                         ##STR20##                                                                    Reagents       MW        Moles   Amount                                       ______________________________________                                        methyl β-D-                                                                             194.18    0.103   20.0  g                                      galactopyranoside                                                             Sigma Chemical Co.,                                                           (No. M-6757)                                                                  Phosphate Buffer, 100 mM                                                                     --        --      412.0 ml                                     Catalase, 16900 units/mg                                                                     --        --      7.5   mg                                     Sigma Chemical Co.,                                                           (No. C-40)                                                                    Galactose Oxidase                                                                            --        --      9000  units                                  ______________________________________                                    

The reaction is conducted in a one liter vessel equipped with an aeratorand a gentle stirrer. Sterile conditions are used to prevent enzymedeactivation by microbial contamination. The reaction is run at 4° C. tominimize deactivation of galactose oxidase.

Methyl β-D-galactopyranoside (1) is dissolved in the aerated phosphatebuffer. The volume flow of air discharged by the aerator is regulated toproduce an oxygen saturated solution while preventing foaming of thesolution. At 4° C., the galactose oxidase and catalase are added andthis solution is aerated for 20 hours.

The enzymes are removed from the product solution by ultrafiltrationusing a 10,000 MWCO membrane (Diaflo 13242, manufactured by Amicon). Theresulting filtrate contains the oxidation product, methylβ-D-galacto-hexodialdo-1,5-pyranoside (2).

2. Condensation of Oxidation Product With Formaldehyde to Methyl5-C-Hydroxymethyl-α-L-arabino-hexopyranoside (3)

    ______________________________________                                         ##STR21##                                                                    Reagents                  Amount                                              ______________________________________                                        filtrate solution containing the                                                                        400 ml                                              oxidation product methyl β X.sup.-  D-galacto-                           hexodialdo-1,5-pyranoside from step 1.                                        37% formaldehyde solution (aqueous)                                                                     400 ml                                              50% sodium hydroxide solution (aqueous)                                                                 144 ml                                              ______________________________________                                    

The filtrate solution from step 1 and the formaldehyde solution arecombined in a one liter vessel. The sodium hydroxide solution is addedto the filtrate/formaldehyde solution over a period of 1 hour while thesolution temperature is maintained between 20° C. and 25° C. with anice-water bath. After the exothermic reaction has ceased, the ice-waterbath is removed and the reaction mixture is stirred at room temperaturefor 16 hours. The reaction mixture is heated to 55° C. and deionizedusing ion exchange columns: first Amberlite IR-120(H⁺), then AmberliteIRA-400(OH⁻), both packings manufactured by Rohm & Haas. Finally, thedeionized solution of the product is eluted through an Amberlite IRA-400(HSO₃ ⁻) ion exchange column to remove remaining formaldehyde. Slow roomtemperature evaporation to dryness, followed by drying of the residue atroom temperature under vacuum overnight produces 18.5 g (80%) of (3).

EXAMPLE II Preparation of1,6-anhydro-5-C-hydroxymethyl-β-L-altropyranose (4) ##STR22##

Methyl 5-C-hydroxymethyl-α-L-arabino-hexopyranose (3) (59.0 g, 0.263moles) is dissolved in 0.70M sulfuric acid (260 ml), and stirred at 100°C. for 90 minutes. The solution is cooled to room temperature andneutralized using an ion exchange resin (Amberlite IRA-400 (OH⁻). Theresin is filtered off, and the filtrate is refluxed for 15 minutes withactivated carbon (4.0 g). Carbon is removed with a glass fiber filter,and the filtrate is evaporated to dryness with ethanol. The white waxyresidue is refluxed for 15 minutes with methanol (50 ml). The solutionis stored overnight at 0° C. The product is filtered to yield 20.0 g(39.6%) of 1,6-anhydro-5-C-hydroxymethyl-β-L-altropyranose (4).

M.P.=166.5° C.-168.5° C.

[α]_(D) ²³ =+145.1 (C 7.2 in water).

Preparation of 5-C-hydroxymethyl-L-arabino-hexofuranose (8) ##STR23## 1.Preparation of5-(acetoxymethyl)-1,2,3,4,6-penta-O-acetyl-L-arabino-hexopyranose (7)

A solution of crude 1,6-anhydro-5-C-hydroxymethyl-β-L-altropyranose (5)(10.0 g, 52 mmol) in a mixture of acetic anhydride (100 ml) and pyridine(100 ml) is stirred at room temperature for 3 hours. The reactionmixture is poured into ice water (300 ml), the product is extracted withmethylene chloride (300 ml). The organic phase is washed with 1M HCl(3×400 ml), sodium bicarbonate (300 ml) and water (300 ml).

Evaporation of solvent produces crude 19.0 g of5-C-acetoxymethyl-1,6-anhydro-2,3,4-tri-O-acetyl-β-L-altropyranose (6)which, without further purification, is dissolved in acetic anhydride(300 ml) and the solution is cooled to 0° C. While maintaining thistemperature, sulfuric acid (30.0 g) is slowly added. When the additionis complete, the ice bath is removed and the solution is stirred atambient temperature for 2 hours. At that time, TLC (Analtech GF plates,toluene:acetone 2:1) shows a single major product with a small amount ofmore polar impurities. An excess of acetic anhydride is destroyed byslow addition of water (45 ml) with cooling at temperature below 30° C.The resulting solution is partitioned between methylene chloride (300ml) and aqueous sodium bicarbonate (300 ml), the organic phase is washedrepeatedly with sodium bicarbonate (3×300 ml) and water (300 ml).Evaporation of the solvent gives 17.0 g (70% yield) of (7).

[α]_(D) ²⁶.2 =+39.5° (C8.3 in CHCl₃)

Anal. calc. for C₁₉ H₂₆ O₁₃ : C, 49.35; H, 5.67. Found: C, 49.16; H,5.60.

2. Preparation of 5-C-Hydroxymethyl-L-arabino-hexofuranose (8)

A solution of5-C-(acetoxymethyl)-1,2,3,4,6-penta-O-acetyl-L-arabino-hexopyranose (7)(4.0 g, 8.7 mmol) in 0.05M methanolic sodium methoxide (50.0 ml) isstirred at room temperature for 2 hours. The reaction mixture isdeionized with Amberlite IR-120 (H⁺) and evaporated to oily residue.Purification on a silica column with chloroform:methanol (4:1) followedby chloroform:methanol (3:2) gives 0.5 g (27%) of (8).

EXAMPLE IV Preparation of ethyl5-C-hydroxymethyl-L-arabino-hexofuranoside (9) andethyl-5-C-hydroxymethyl-L-arabino-hexopyranoside (10) ##STR24##

A solution of hydrogen bromide in acetic acid, prepared by slow additionof acetic anhydride (30 ml) to 48% HBr (8 ml) at 15°-30° C., is added to5-acetoxymethyl-1,2,3,4,6-penta-O-acetyl-L-galactopyranose (7) (2.5 g,5.1 mmol) and is stirred for 2.5 hours at room temperature. The reactionmixture is then partitioned between ice-cold water and methylenechloride. The organic layer is deacidified with a saturated sodiumbicarbonate solution and washed with cold water. After drying withanhydrous sodium sulfate, the solvent is evaporated at 25°-30° C. to abrown residue which is further dried under high vacuum for 30 minutes.This residue, without further purification, is treated with mercuriccyanide (0.6 g, 2.3 mmol) in absolute ethanol (40 ml) for 2 hours at 50°C. After evaporation of the solvent, the residue is dissolved inchloroform, washed with an aqueous sodium bicarbonate solution. Thechloroform solution is dried with anhydrous sodium sulfate andevaporated to dryness. The residue is deacetylated with 0.05M MeONa/MeOHsolution, giving a mixture of two major products which are separated ona silica column with chloroform:methanol (4:1). The faster movingcompound is ethyl 5-C-hydroxymethyl-L-arabino-hexofuranoside (9) 0.25 g(20.5%) and the slower moving product is methyl5-C-hydroxymethyl-L-arabino-hexopyranoside (10) 0.1 g (8.2%).

EXAMPLE V Preparation of methyl5-C-hydroxymethyl-α-D-xylo-hexopyranoside (13) ##STR25## whereBn=benzyl. 2,3,4-tri-o-benzyl-methyl-α-D-gluco-hexodialdo-1,5-pyranoside(11) (12.0 g, 0.025 moles) is dissolved in 1,4 dioxane (320 ml) andadded to a solution of 1M NaOH (130 ml) and 37% CH₂ O (130 ml). Thissolution is stirred overnight (20 hours), neutralized with formic acidand evaporated. The remaining oily residue is dissolved in CH₂ Cl₂ (50ml), washed with 2×50 ml H₂ O, dried with NaSO₄, and evaporated. Theproduct is purified on 100 ml of silica gel with an ethyl acetate:hexanesolvent system, 45:55 (vol/vol). Two fractions are collected. The secondfraction is methyl5-C-hydroxymethyl-2,3,4-tri-o-benzyl-α-D-xylo-hexopyranoside (12) (5.75g (45%)). The compound (12) (5.5 g, 0.0112 moles) is dissolved in 50%methanol (50 ml), acetic acid (15 ml), and treated with palladiumhydroxide (6.0 g), and hydrogen gas (P=1 Atm.), for 20 hours. Thesolution is then filtered, deionized using ion exchange resin AmberliteIRA-400 (OH-) (15 ml), and evaporated. The remaining oil is methyl5-C-hydroxymethyl-α-D-xylo-hexopyranoside (2.4 g, 98%) (13). EXAMPLE VIPreparation of 1,6-anhydro-5-C-hydroxymethyl-β-L-idopyranoside (14)##STR26##

Methyl-5-C-hydroxymethyl-α-D-xylo-hexopyranoside (13) (100 mg., 0.00045moles) is treated with 0.375M sulfuric acid (0.75 moles). The solutionis kept at 100° C. for 90 minutes, cooled and neutralized with ionexchange resin Amberlite IRA-400 (OH-) (15 ml). The solution is filteredand evaporated to give 50 mg of1,6-anhydro-5-C-hydroxymethyl-β-L-idopyranoside (14) (65%).

EXAMPLE VII Preparation of 5-C-hydroxymethyl-D-lyxo-hexopyranose (16)and 1,6-anhydro-5-C-hydroxymethyl-β-L-gulose (17). ##STR27##

1,2,3,4-tetra-D-benzyl-5-C-hydroxymethyl-L-lyxo-hexopyranose (15) (9 g,0.0158 mole) is dissolved in methanol (50 ml) and added to water (50 ml)containing palladium hydroxide on carbon (9 g, Aldrich 21,291-1). Themixture is hydrogenated under atmospheric pressure for 16 hours. After acareful evacuation of hydrogen and flushing with nitrogen, the reactionmixture is heated on a steam bath for 15 min. The catalyst is removed byfiltration. Evaporation of the filtrate produces 3.1 g of a crudemixture of α and β isomers of 5-C-hydroxymethyl-L-lyxo-hexopyranose(16). This product (2.5 g,16) is dissolved in 0.5M sulfuric acid andstirred at 100° C. for 90 min. After cooling to room temperature, thesolution is neutralized with IRA-400(OH), treated with charcoal (0.5 g),filtered and evaporated. TLC examination of the solution, done on theWhatman KF plates with acetonitrile/water mixture 8:2, reveals thepresence of 1,6-anhydro-5-C-hydroxymethyl-β-L-gulose (17) as well as5-C-hydroxymethyl-L-lyxohexopyranose (16).1,6-anhydro-5-C-hydroxymethyl-β-L-gulose (17), is separated using silicacolumn (Matrex silica 60 A, Amicon Corp.) and eluent chloroform/methanol8:2. Yield of the product (17) is 0.9 g.

EXAMPLE VIII Preparation of 5-C-hydroxymethyl-α-L-arabino-hexopyranosyl(1→6)-D-galactopyranose and -galactofuranose. 1. Preparation of5-C-acetoxymethyl-2,3,4,6-tetra-O-acetyl-α-L-arabino-hexopyranosylbromide (18) ##STR28##

Glacial acetic acid (60 ml) is saturated with dry gaseous HBr for 30minutes at 18°-20° C. This solution is mixed with5-C-acetoxymethyl-1,2,3,4,6-penta-O-acetyl-L-arabino-hexopyranose (7)(6.0 g, 0.013 ml) and is stirred at an ambient temperature for 3.5hours. Workup of the reaction mixture involves: dilution with methylenechloride (150 ml), washing with ice-water, sat. sodium bicarbonatesolution, and water again. After drying the methylene chloride solutionwith sodium sulfate (anhydrous), evaporation of the solvent producescrude 5-C-acetoxymethyl-2,3,4,6-tetra-O-acetyl-α-L-arabino-hexopyranosylbromide (18) (3 g) which is dried under high vacuum for 30 minutes andis used for the glycosidation reactions without further purification.

2. Preparation ofO-(5-C-hydroxymethyl-α-L-arabino-hexopyranosyl)(1→6)-1,2:3,4-diisopro-pylidene-α-D-galactopyranose(20) ##STR29##

Crude 5-C-acetoxymethyl-2,3,4,6-tetra-O-acetyl-L-arabino-hexopyranosylbromide from step 1 (18) (3.0 g),1,2:3,4-diisopropylidene-α-D-galactopyranose (19) (5.25 g, 20 mmol),mercuric cyanide (2.0 g, 8 mmol) in dry dichloroethane (120 ml) arereacted overnight at 40° C.

After evaporation of the solvent, the residue is dissolved inchloroform, and washed with an aqueous sodium bicarbonate solution(saturated). The chloroform solution is dried with anhydrous sodiumsulfate and evaporated to dryness. The residue is deacetylated with0.05M MeONa/MeOH solution. Yield 1.75 gO-(5-C-hydroxymethyl-α-L-arabino-hexopyranosyl)(1→6)-1,2:3,4-diisopropylidene-α-D-galactopyranose (20).

3. Preparation of O-(5-C-Hydroxymethyl-α-L-arabino-hexopyranosyl(1→6)-D-galactopyranose (21) andO-(5-C-hydroxymethyl-α-L-arabino-hexopyranosyl (1→6)-D-galactofuranose(22) ##STR30##

O-(5-C-hydroxymethyl-α-L-arabino-hexopyranosyl)-(1→6)-1,2,3,4-diisopropylidene-α-galactopyranose(20) (1.75 g) is stirred in acetic acid 75% (30 ml) at 80° C. for 3hours. The slightly yellow solution is treated with charcoal and cooledto room temperature. Filtration and evaporation of solvent is followedby crystallization of the residue from acetic acid gives 0.7 g (50%) ofthe mixture of (21) and (22).

EXAMPLE IX 5-C-hydroxymethylation of lactitol 1. Enzymic Oxidation ofLactitol

    ______________________________________                                         ##STR31##                                                                     ##STR32##                                                                    Reagent                 Amount                                                ______________________________________                                        Lactitol (23)           20.0   g                                              (manufactured by CCA BioChem)                                                 Phosphate Buffer, 100 mM, pH 7                                                                        232.0  ml                                             Catalase (Sigma), 16900 u/mg                                                                          7.00   mg                                             Galactose Oxidase       9000   units                                          ______________________________________                                    

The reaction is conducted in a vessel equipped with a gentle stirrer andan aerator. Sterile conditions are used to prevent enzyme deactivationby microbial contamination. The reaction is run at 4° C. to minimizedeactivation of galactose oxidase.

Lactitol (23) is dissolved in the aerated phosphate buffer. At 4° C.,the galactose oxidase and catalase are added and this solution isaerated to maintain oxygen saturation for 20 hours.

The enzymes are removed from the product solution by ultrafiltrationusing a 10,000 MWCO membrane (Diaflo 13242, manufactured by Amicon). Theresulting filtrate contains the oxidation product (24).

2. Condensation of Oxidation Product With Formaldehyde

    ______________________________________                                         ##STR33##                                                                    Reagents                  Amount                                              ______________________________________                                        filtrate solution containing the                                                                        400 ml                                              oxidation product (24) from step 1                                            37% formaldehyde solution 400 ml                                              50% sodium hydroxide solution (aqueous)                                                                 144 ml                                              ______________________________________                                    

The filtrate solution and the formaldehyde solution are combined in aone liter vessel. The sodium hydroxide solution is added tofiltrate/formaldehyde solution over a period of 1 hour while thesolution temperature is maintained between 20° C. and 25° C. with anice-water bath. After the exothermic reaction has ceased, the ice-waterbath is removed and the reaction mixture is stirred at room temperaturefor 16 hours. The reaction mixture is heated to 55° C. and deionizedusing ion exchanger columns: first Amberlite IR-120 (H+), then AmberliteIRA-400 (OH-). Finally, the deionized solution of the product is elutedthrough a column with Amberlite IRA-400 (HSO₃ -) in order to removeremaining formaldehyde. Evaporation to dryness followed by drying theresidue at room temperature under vacuum overnight produces 11.9 g (55%yield) of 5-C-hydroxymethyl-α-L-arabino-hexopyranosyl-D-glucitol (25).

The 5-C-hydroxymethylation of galactosyl groups described above isreadily adapted by one skilled in the art to other di-, tri- andoligosaccharides containing at least one galactosyl group. Applicablestarting compounds for this type of 5-C-hydroxymethylation are raffinose(i.e., O-α-D-galactopyranosyl-(1→6)-α-D-glucopyranosyl-β-D-fructofuranoside), stachyose(i.e.,O-α-D-galactopyranosyl-(1→6)-O-α-D-galactopyranosyl-(1.fwdarw.6)-α-D-glucopyranosyl-α-D-fructofuranoside),arabino- galactan and D-galactopyranosyl glycerols.

EXAMPLE X Preparation of brownies containing5-C-hydroxymethyl-α-L-arabino-hexopyronosyl-D-glucitol.

    ______________________________________                                        Ingredient               Amount (gms)                                         ______________________________________                                        5-C-hydroxymethyl-α-L-arabino-hexopyranosyl-                                                     309.8    g                                           D-glucitol (as prepared in Example IX)                                        Flour                    152      g                                           Vegetable shortening     50       g                                           Cocoa                    35.3     g                                           Starch                   11.7     g                                           Conventional additives (flavors and a small                                                            6.2      g                                           amount of baking soda)                                                        Eggs                     50       g                                           Oil                      63       g                                           Water                    80       g                                           ______________________________________                                    

The ingredients are stirred with a large spoon until well blended (about50 strokes or 1 minute) to form a batter. The batter is poured into alightly greased 13"×9"×2" pan, and then baked at 350° F. for about 26.5minutes to produce the finished brownies.

EXAMPLE XI Preparation of cookies containing1,6-anhydro-5-C-hydroxymethyl-β-L-altropyranose.

    ______________________________________                                        Ingredients             Amounts (gms)                                         ______________________________________                                        1,6-anhydro-5-C-hydroxymethyl-β-L-                                                               176                                                   altropyranose (as prepared in Example II)                                     Table Sugar (i.e., sucrose)                                                                           176                                                   Flour                   328                                                   Shortening              196                                                   Egg                      96                                                   Water                    20                                                   Conventional additives (flavors and a small                                                            8                                                    amount of baking soda)                                                        ______________________________________                                    

The ingredients are combined and the resulting dough is kneaded untiluniform. Dough balls (10-13 gm) are individually placed on a lightlygreased cookie tray and then baked at 350° F. for 7-8 minutes to producefinished cookies.

EXAMPLE XII Preparation of a white cake containing5-C-hydroxymethyl-α-D-xylo-hexopyranoside

    ______________________________________                                        Ingredients             Amount (gms)                                          ______________________________________                                        5-C-hydroxymethyl-α-D-xylo-hexopyrano-                                                          133                                                   side (as prepared in Example V)                                               Cake flour              107                                                   Erythritol tetraester of olive oil                                                                    47.5                                                  fatty acid (a polyol polyester used                                           used as a shortening)                                                         Double-acting baking powder                                                                           6.7                                                   Milk                    130                                                   Egg whites              60                                                    Vanilla                 2.5                                                   ______________________________________                                    

The ingredients are stirred with an electric mixer to form a uniformbatter. The batter is poured into a lightly greased 13"×9"×2" pan, andthen baked at 350° F. for 40 minutes to produce the finished white cake.This cake looks and tastes like a conventional white cake, but hasnearly no caloric value.

EXAMPLE XIII Sugar Substitute Compositions

The following list exemplifies sugar substitute formulations whichprovide sweetness and bulk similar to sucrose.

(a) 0.4% aspartame and 99.6% methyl5-C-hydroxymethyl-α-L-arabino-hexopyranose

(b) 0.5% aspartame and 99.5%1,6-anhydro-5-C-hydroxymethyl-β-L-altropyranose

(c) 0.3% saccharin and 99.7% 5-C-hydroxymethyl-β-D-xylohexopyranose

(d) 49.5% 5-C-hydroxymethyl-β-D-xylo-pyranosyl-β-D-fructofuranoside,49.4% sucrose, and 0.1% aspartame.

(e) 49.5% 5-C-hydroxymethyl-α-L-arabino-hexopyranosyl-D-glucitol, 49.4%polydextrose, and 0.1% aspartame

EXAMPLE XIV Methyl 1-O-benzyl-α-D-fructofuranoside (26) and methyl1-O-benzyl-D-fructofuranoside (27)

2,3:4,5-diisopyropylidene-α-fructopyranose (15.0 g, 57.6 mmole) isdissolved in dry dimethylformamide (250) containing benzyl chloride(11.05 ml, 96 mmole). When the exothermic reaction ceases, the mixtureis stirred at room temperature for 1.5 hours. Any excess hydride isdecomposed with methanol, and the pH is adjusted to neutral with aceticacid. Filtration and evaporation of solvents produces 22 g of a crudeoil containing 1-O-benzyl-2,3:4,5-diisopropylidene=α-D-fructopyranose(R_(F) =0.56, Analtech GF plates, toluene:acetone 4:1). This crudemixture is dissolved in 1% iodine solution in methanol (200) ml) and isrefluxed for 24 hours. Sodium bisulfate is added to reduce the iodineand the mixture is filtered. The filtrate is evaporated and the productsare separated on a silica column with chloroform:methanol 20:1. Thecombined fractions give 11.0 g (70%) of a mixture containing a ratio of(26) and (27) to (4C) approx. 2:1. Further chromatography of thisproduct on silica column with chloroform: methanol 6:1 produces 6.55 g(40%) of (26) and (27), combined.

EXAMPLE XV Methyl 1,3,4-tri-O-benzyl-α-D-fructofuranoside (28), andmethyl 1,3,4-tri-O-benzyl-β-D-fructofuranoside (29)

A mixture of methyl 1-O-benzyl-(α+β)-fructofuranosides, (26) and (27)(10.0 g, 35 mmole), triphenylmethyl chloride (12.2 g, 44 mmole),pyridine (90 ml), 4-dimethylaminopyridine (0.1 g) is stirred at 40° C.for 24 hours. The mixture is poured into ice water (400 ml), and theproduct is extracted with ethyl acetate (500 ml). The organic layer iswashed with 1N HCl (2×400 1), saturated sodium bicarbonate, and withwater again (400 ml). The solvent is evaporated and the residue wasdried under high vacuum in the presence of P₂ O₅ overnight. Theresulting orange oil, containing methyl1,3,4-tri-O-benzyl-6-triphenylmethyl-(α+β-fructofuranosides (29), (R_(F)=0.25, analtech GF plates, toluene:acetone 4:1), is benzylated in drydimethylformamide (380 ml) with benzyl chloride (20.1 ml, 175 mmole) and60% sodium hydride (7.0 g, 175 mmole) for 1.5 hours at room temperature.Excess hydride is decomposed with methanol. The pH is adjusted toneutral with acetic acid and the solvent is evaporated. The crudeproduct, a mixture of methyl1,3,4-tri-O-benzyl-6-triphenylmethyl-(α+β)-fructofuranosides (30),(R_(F) 0.11 and 0.16, hexane:ethyl acetate 20:1), is dissolved in amixture of methanol (200 ml), 1,4-dioxane (100 ml) and trifluoraceticacid (75 ml), and is refluxed for 5 hours. The acid is neutralized withNa₂ CO₃, and the solid material is filtered. The filtrate is evaporatedto an oily residue which is dissolved in ethyl ether, washed with water,and is evaporated again. The residue, containing three major compounds,is purified on a silica column (2.5 1) using toluene:acetone 5:1 mixturefor elution. Two main, faster moving products were collected giving 13.5g (83%) of a mixture of (28) and (29).

EXAMPLE XVI Methyl5-C-hydroxymethyl-1,3,4-tri-O-benzyl-β-D-erythrohexulofuranoside (31)and Methyl5-C-hydroxymethyl-1,3,4-tri-O-benzyl-α-D-erthro-hexulofuranoside (32)

An oxidizing mixture is made by a careful addition at -70° C. of a drysolution of dimethylsulfoxide (4.98 ml, 70 mmole) and methylene chloride(30 ml) into a solution of oxalyl chloride (3.04 ml, 35 mmole) in drymethylene chloride (160 ml), and stirring the resulting solution for 10min. While maintaining the temperature -70° C., a solution of methyl1,3,4-tri-O-benzyl (α+β)-fructofuranosides (28, 29) in dry methylenechloride (60 ml) is added over a period of 10 min and stirring iscontinued for an additional 45 min. After subsequent addition of drytriethylamine (20.2 ml, 145 mmole) the reaction mixture is allowed towarm to room temperature. The product (aldehyde) solution is washed withwater (50 ml), 1N HCl (200 ml), saturated sodium bicarbonate and water(200 ml) again. Evaporation of the solvent in vacuo produces a residue,containing methyl 1,3,4-tri-O-benzyl-(α+β)-D-fructofuranose-6-guloside(33), which is dissolved in 1,4-dioxane (250 ml). The hydroxymethylationreaction is initiated by adding to this solution 37% formaldehyde (44ml) and 1M sodium hydroxide (44 ml). The mixture is stirred at roomtemperature for 20 hours, neutralized with 1N HCl and evaporated todryness. The residue is fractionated on a silica column using a mixtureof toluene:acetone 10:1. Yields: α=isomer (32) 2.25 g (15.7%), β-isomer(31) 1.75 g (12.2%).

EXAMPLE XVII Methyl 5-C-hydroxymethyl-α-D-erythro-hexulofuranoside (34)

5-C-hydroxymethyl-1,3,4-tri-O-benzyl-α-D-erythro-hexulofuranoside (32)(2.25 g, 4.5 mmole) is hydrogenated (atmospheric pressure, roomtemperature) in methanol in the presence of 20% palladium hydroxide oncharcoal (3.0 g), for 20 hours. The reaction mixture is filtered throughCelite. The cake is washed with hot water, and the filtrate isevaporated to dryness producing quantitative yield, 1.15 g. of (34).

Methyl 5-C-hydroxymethyl-α-D-erythro-hexulofuranoside (35)

Methyl 5-C-hydroxymethyl-1,3,4-tri-O-benzyl-β-D-erythrohexulofuranoside(31) (1.75 g, 2.5 mmole) is exposed to the procedure identical to thatfor making the α-isomer. Yield of (35), 0.8 g (100%).

What is claimed is:
 1. A 5-C-hydroxymethyl hexose compound wherein oneor more of the hydroxyl groups is esterified with a carboxylic acid. 2.A compound according to claim 1 wherein said carboxylic acid is an alkylcarboxylic acid.
 3. A compound according to claim 2 wherein 3 or morehydroxyl groups are esterified.
 4. A compound according to claim 3wherein said 5-C-hydroxymethyl hexose is covalently bonded through aglycosidic linkage to a monosaccharide or a disaccharide.
 5. A compoundaccording to claim 4 wherein 4 or more of the hydroxyl groups areesterified.
 6. A 5-C-hydroxymethyl hexose compound wherein one or moreof the hydroxyl groups is converted to an ether moiety.
 7. A compoundaccording to claim 6 wherein said ether moiety comprises an alkyl group.8. A compound according to claim 6 wherein said 5-C-hydroxymethylcompound is covalently bonded through a glycosidic linkage to amonosaccharide or a disaccharide.
 9. A compound according to claim 2wherein said carboxylic acid is a lower alkyl carboxylic acid.
 10. Acompound according to claim 1 wherein said carboxylic acid is an arylcarboxylic acid.
 11. A compound according to claim 10 wherein saidcarboxylic acid is benzyl carboxylic acid.
 12. A compound according toclaim 7 wherein said ether moiety is a lower alkyl group.